Hydroxynaphthoic acid amide coupler



Patented Mar. 9, 1943 Q I j 2,313.586

UNITED STATES PATENT. OFFICE Ilmari F. Sahninen, Arnold Weissherger, andDudley B. Glass, Rochester. N. Y., assignors to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey No Drawing. ApplicationOctober 15, 1940, Se-

rial No. 361,262. In Great Britain February 20, 1940 4 Claims. (CI.95-88) This invention relates to color-forming devel- 'ble to heat andlight than the corresponding opment and particularly to novel couplingcomamides derived from primary amines. ponents for producing coloredimages. The compounds which we propose to use have It is known thatcolored photographic images 'the following formula: may be formed byusing a developer which forms 5 0 a colored compound on development. Thecolored compound thus formed is deposited adja- R cent to the silvergrains of the silver image dur- 0 ing the development. It is also knownthat a colored image may be formed, by adding to certain developersolutions or by incorporating in V the gelatino-silver-halide emulsionbefore or aftw i d R'=a,1ky1, aryl, aralkyl.

er exposure a compound which couples during de- Specific compounds whichmay be used velopment with the oxidation product of the cording t our iv ti n are the following:

developing agent and forms a coloring substance V I which is likewisedeposited adjacent to the silver Cm grains of the silver image duringdevelopment. I

Such a compound, which is employed in conjunc- I O tion with adeveloping agent for the silver and v v which couples with the oxidationproduct thereof 2 during development, is referred to herein as a I.

coupling component or coupler. Y l'hydmxy'zmphmic'N'mthylHide Thepresent invention concerns new or improved color forming developerscomprising a l 02m primary aromatic amino compound, serving as (2) (F111the developing agent, and a coupler as hereinafter defined and alsoincludes a new or improved color development process which consists inde- 7 veloping a reducible silver salt image in a photo- 1 h dxy-?,(N-ethy1, N-s-mphthyl) naphth mlde graphic element with the aid ofa primary aromatic amino compound in the presence of a cou- 0H pler ashereinafter defined. It also includes pho- I CnHn tographic sensitiveelements having such a coupler incorporated in one or more emulsionlayers. In British Patent 503,752 carboxylic acid amide couplers aredescribed which are obtained by the reaction of a-naphthol carboxylicacid chloride with amines containing a high molecular substituent group.In these couplers the hy- OH droxyl group of the naphthol constitutesthe di- 40 3 0 recting group inthe coupling reaction. and the a 00 N Icarbon atom of 'the carboxylic acid amide group (4) is, therefore,directly attached to the coupler porf OWE;

tion of the molecule, and the amide may be con-' sidered as beingderived from a primary amine. 5

While these compounds form colored photo- (a) CO-N graphic images upondevelopment in primary 1 hydroxy MN iilfilfi' ilnfifii aromaticraminodevelopers, the coupler molecule J 0H p in certain cases is unstable toheat and light I cmcmcgro and is unsatisfactory for that reason. (5) cWe'have found. that hydrcxynaphthoic acid amide couplers in which theamide may be con-- 7 Q sidered as being derived from a secondary aminepossess more desirable light absorption charac- 1J1 dm he l h teristicsfor color photography and are more statiiifi my!) mph l-hydrory2-(N-amyhN-a-naphthyhnaphthamide l-hydroxy-2-(N-i5obutyiN-p-amylbenzene) naphthai'nide CsHu t 9 wee-N cm co-zi-O 4oN-methyl-5-hydroxymphthanilidci-hydroxy-Z-(N-isobutyl-N-psoc-amylbcnzmc)-naphtliamidel-hydroxy-fl-(N-banzyi-N-lp-swwamyll bcmne)-naphthamide 65i-hydrouy-a-(N-n-cmyl-N-emphthyb-mphmidc I 75 in. cmcmcn.

CHr- H-CH2CH:CH3 l-hydroxy-2-(N-n-amyl-N-psec.-amylbenzene)-naphthamideC O-N C HaC H2O H:- C Ha-lH-CHaC HrCHs 7 l-hydroxy-2-(N-[-pheny1]pr6py1-N-p-sec.-amylbonzene) naphtham his c O-N-CHIC morn-O5'-hydroxy-l-(N-phenyl-Nfi-phenyl-propyl)-naphtharnide The couplers maybe prepared by the reaction of secondary amines withthe acid chloridesof hydroxynaphthoic acids, with the acid chlorides 01 their esters andsubsequent hydrolitic elimination of the acid groups, or with theiresters. These reactions can also be applied to the substitution productsof the hydroxynaphthoic acids with suitable substituents in one or bothrings or the reaction products can be substituted, for example, withchlorine. The couplers made according to our invention may be dissolvedin the developing solution or may be incorporated in the emulsion layeraccording to their solubility characteristics. Compounds 2 to 9 and 11to 16 are suitable for use in the emulsion layer and the remainingcompounds are sufllciently soluble for use in the developing solution.The use of an alcohol in the developer which is a solvent for thecoupler improves the color produced particularly when the coupler is inthe layer.

These couplers contain a phenolic hydroxyl group which is reactive withthe oxidation prod-v uct of a primaryaromatic amino coupling developingagent to form colored images. The compounds are presumably active in theortho or para position with respect to-the position of the hydroxylgroup.

The coupling compounds used according to our invention may contain othersubstituents which do not affect the coupling properties of thecompound. For example, the naphthol portion of the coupler may containsubstituent groups and may even contain readily replaceable groups suchas chlorine or bromine in the position ortho or' para with respect tothe hydroxyl group where such substituents do not affect the couplingprop erties. Where we refer in the general formula to aryl and-aralkylgroups, it is to be understood I that these groups maybe furthersubstituted.

The aromatic amino developing agents used with the coupler compounds ofour'invention include the mono-, diand tri-aminoarylcompounds and theirderivatives formed by substitution in the amino group as well as in thering, such as alkylphenylenediamines and alkyltoluylenediamines. Thesecompounds are usually used in the salt form, such as the hydrochlorideor the sulfate, which are more stable than the amines themselves.Suitable compounds are diethyl-p-phenylenediamine hydrochloride,monomethyl-p-phenylenediamine hydrochloride,dimethyl-p-phenylenediaminehydrochloride and dimethyl-p-phenylenediaminesulfate. The paminophenols and their substitution products may also beused where the amino group is substituted. All of these compounds havean unsubstituted amino group which enables the oxidation products of thedeveloper to couple with the color forming compounds to form a dyeimage.

The following developer formula may be used with the compounds of ourinvention:

A; p-Aminodiethylaniline sulfate grams 2 Sodium sulfite anhydrous do, 5Sodium carbonate anhydrous do 20 Potassium bromide do. 2 Water to liter1 B. Coupler "grams-.. 1to5 Isopropyl alcohol -cc 100 Bisadded toA.:

In case the coupler isincorporated in the emulsion layer, the alcohol inthe developer acts as a solvent for the coupler and improves the color.Our development process may be'employed'for the production of coloredphotographic images in layers of gelatin or other carrier such ascollodion, organic esters of cellulose or synthetic resins. The carriermay be supported by a transparent medium such as glass, a celluloseester, or a non-transparent reflecting medium such as paper of an opaquecellulose ester. The emulsion may be coated as a single layer on thesupport or as superposed layers on one or both sides of the support. Thesuperposed layers may be diflerentially sensitized to formznatural colorphotographic images in the well known manner.

The examples and compounds set forth in the present specification areillustrative only and it is to be understood that our invention islimited only by the scope of the appended claims.

We claim:

1. A color forming photographic developer comprising a primary aromaticamino developing agent and a coupler compound having the formula:

' where R is an aryl radical and R is an aralkyl radical. 1

2. The method of producing a colored photographic image in a gelatinosilver halide emulsion layer which comprises exposing the layer anddeveloping it with a primary aromatic amino developing agent in thepresence of a coupler compound having the formula:

. on I CON\ where R is an aryl radical and R is an arallryl radical.

3. A color-forming photographic developer or:v

I CON\ R,

where R is an aryl radical and R is an aralkyl radical.

4. The method of producing a. colored photographic image in agelatino-silver halide emulsion layer which comprises exposing the layerand developing it with a primary aromatic amino developing. agent in thepresence of a coupler compound having the formula:

/R v CON\ I radical.

aryl radical and R. is an aralkyl

